Additives and methods for reducing odor

ABSTRACT

Additives and methods for reducing or eliminating odor in oil based media. The additives comprise an essential oil, an essential oil component, or mixtures thereof.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to additives and methods for reducing odor in oilbased media, and to oil based media mixtures having reduced odor.

2. Description of the Related Art

Asphalt, representing one example of oil based media, is an importantmaterial for building and repairing roads. It is also used inapplications such as roofing and weather sealing. It is well known,however, that hot mix asphalt produces volatile materials such ashydrocarbons, sulfides, and mercaptans, which can have strong,persistent and potentially harmful odors. The odors can cause discomfortto persons working with the hot asphalt, to residents living near areaswhere asphalt is manufactured or paved and generally to persons who comewithin close range of the hot asphalt.

Traditional odor treating compositions act as deodorizers or maskingagents, essentially overwhelming the undesired odor with another odor.Such techniques, however, are poor at masking strong odors. In addition,masking does not reduce the concentration of the volatiles causing theodors, and therefore is generally ineffective at reducing the harmfuleffects of the volatiles.

There exists a need, therefore, for new compositions and methods forreducing the odors of oil based media.

BRIEF SUMMARY OF THE INVENTION

The invention provides a method for reducing odor in oil based media,said method comprising mixing an odor reducing amount of an odorreducing additive with the oil based medium, wherein the odor reducingadditive is an essential oil, an essential oil component, or mixturesthereof.

The invention also provides mixtures having reduced odor comprising: anoil based medium; and an odor reducing additive, wherein the odorreducing additive is an essential oil, an essential oil component, ormixtures thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a GC trace of a blank sample showing a volatile substancegiven off by septa when heated to 151° C.

FIGS. 2, and 3 are GC traces of the headspace above an asphalt sample.

FIG. 4 is a GC trace of the headspace above an asphalt sample containingan odor reducing additive.

FIG. 5 is a GC trace of the headspace above an asphalt sample containingan odor reducing additive.

FIG. 6 is a GC trace of the headspace above an asphalt sample.

FIG. 7 is a GC trace of the headspace above an asphalt sample containingan odor reducing additive.

FIG. 8 is a GC trace of the headspace above an asphalt sample containingan odor reducing additive.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The invention provides odor reducing additives and methods for reducingodors in oil based media.

The odor reducing additive is one or more essential oils or essentialoil components. By “essential oils” is meant natural extracts of variousparts of aromatic plants and trees. By “essential oil components” ismeant any of the components which make up an essential oil. Examples ofsuch components include, but are not limited to, terpenes, alcohols,aldehydes, aromatics, phenolics, esters, terpene derivatives, nonterpene essential oil components, and terpene reactants.

Preferred odor reducing additives are terpenes, or essential oilscontaining terpenes as components. As used herein, the term “terpenes”encompasses all variations of terpenes and their derivatives, includinghydrocarbon terpenes, unsaturated terpenes, oxygen containing terpenes(terpenoids) such as alcohols, aldehydes, ketones, esters, acetates,ketals and oxides, as well as terpenes of various chain lengths,including monoterpenes, sesquiterpenes, diterpenes, triterpenes, andtetraterpenes.

Many terpenes occur naturally in plants as constituents of essentialoils or they may form from the process of extraction (such as steamdistillation, water distillation, hydro distillation or solventextraction) of the oil from the plant material. Terpenes may be formedby further processes such as the result of oxygen or hydroxyl additionvia acid hydrolysis or by air oxidation or via synthetic or naturalreagents. In the additives and methods of the invention, the terpenescan be isolated from the oils in order to intensify the terpenes'effectiveness, or essential oils may be used in their whole, especiallywhere the oils naturally contain high concentrations of terpenes.

Examples of essential oils suitable for use in the invention include:ajowan, angelica root, angelica root himalayan, angelica seed, aniseedchina star, anise seed, aniseed, armoise, artemisia, asafoetida,backhousia anisata, lemon myrtle oil certified, basil, basil australian,basil sweet linalool, basil methyl chavicol, bay west indies, bergamotcalabrian, bergamot ivory coast, bergamot mint, bergamot non-phototoxic,borneo camphor, buchu, cabreuva, cajeput ambon, camphor white oil,cananga, caraway, cardamon, carrot seed, carrot seed european, cassia,cedarwood atlas, cedarwood chinese, cedarwood himalayan, cedar leaf,cedarwood texas, cedarwood virginian, celery seed, chamomile germanextra blue, chamomile wild moroccan, chamomile matricaria, chamomileroman, cinnamon bark, cinnamon leaf, cistus, citronella ceylon,citronella java, clary sage french, clary sage bulgarian, clary sage,clove bud, clove bud madagascar extra, clove leaf, clove stem, copaiba,coriander, cubeb, cumin, cypress provence, cypress wild, cypress whitewood, dill seed, elemi, eremophila, buddawood, eucalyptus australiana,eucalyptus blue mallee bush still, eucalyptus blue gum, eucalyptus dives“c”, eucalyptus radiata, eucalyptus staigeriana, everlasting oil, fennelsweet, fennel wild tasmanian, fir needle, siberian, fir needle, canada,fir needle, silver, frankincense, frankincense somalia, galbanum,garlic, geranium, geranium bourbon reunion, geranium bourbon china,geranium egyptian, ginger, ginger fresh, grapefruit australian,grapefruit pink, guaiacwood, gurjun balsam oil, ho leaf, hyssop, juniperbranch, juniperberry extra, juniperberry wild himalayan, juniperberrywild tyrol, kanuka, laurel leaf, lavender, lavender french alpine,lavandin, lavender bulgarian, lavender french population, lavender trueoil, lavandid absolute, lavender spike spanish, lavender tasmanian,lemon cold pressed, lemongrass cochin, lemongrass guatemalan, lemongrassnepal, lemon scented eucalyptus, lemon scented tea tree, lemon verbenagenuine, lime cold pressed, lime distilled, lime west indian distilled,litsea cubeba, lovage root, mace east indian, mandarin cold pressed,mandarin australian, cold pressed, mandarin sicilian premium, manuka,marjoram majorana, marjoram spanish, melaleuca ericifolia, melissagenuine, melissa oil, melaleuca quinquenervia linalool, melaleucaquinquenervia nerolidol, myrrh, myrtle dalmation, nagarmotha, nerolibigarade, niaouli pacific islands, niaouli australian, nutmeg, olibanum,orange bitter, orange navel, orange sweet, orange valencia, origanum,palmarosa, parsley herb, parsley seed, patchouli, patchouli aceh,patchouli clear, pennyroyal, peppermint arvensis complete, peppermintaustralian, peppermint eucalyptus, peppermint mitcham, pepper black,peppermint yakima, peru balsam oil, petitgrain bigarade, petitgrainbigarade italian, petitgrain mandarin, petitgrain paraguay, pimentoleaf, pine needle, pine extract, pine white, austrian, pinus pumilio,pinus sylvestris, rose otto bulgarian, rose otto moroc, rose ottoturkish, rosemary, rosemary verbenone australian, rosemary moroccan,rosemary spanish, rosemary tunisian, rosemary verbenone oil, rosewoodbrazilian sustainable, sage dalmatian, sage spanish, sandalwood eastindian, sandalwood west indian, sandalwood pacific islands, sandalwoodwest indian, sandalwood western australian, savory summer, savorywinter, spearmint, spearmint premium mid west, spikenard, tagette,tagetes, tangerine, tarragon, tea tree bush still, tea tree oilcertified, tea tree premium, thuja, thyme red, thyme linalool oil, thymethymol oil, thyme wild, tocopherol alpha, turmeric, turpentine, valerianeuropean, valerian indian, vanilla, vetiver, vetiver bourbon, vetiverhaiti, vetiver java, wintergreen natural chinese, wintergreen naturalgaultheria, yarrow, yarrow high chamazulene ct, ylang ylang 1st, ylangylang 3rd, ylang ylang complete, ylang ylang extra, ylang ylang superextra.

Without wishing to be bound by any particular theory, it is believedthat the odor reducing additives of the invention reduce odor byinteracting with odor causing compounds in oil based media. Thuspreferred additives are those that contain components capable ofinteracting with odor causing substances. Such components include forexample: unsaturated terpenes; phenolics such as eugenol (an isolatefrom clove oil; this is not a terpene but is still an essential oilcomponent) which can react for instance with acids and base derivedodors; primary, secondary, and tertiary alcohols such as linalool,citronellol, terpineol and especially tertiary alcohols, which can formodor reactive carbocations; oxides, such as 1,4 cineole, 1,8 cineole,and linalool oxide; ketones such as camphor, a common constituent ofessential oils like Rosemary and Sage oil or it may be manufactured as aderivative of turpentine oil.

Odor reducing additives can also be selected for a particularapplication based on the ability of the components in the additive todissolve or bind odorous compounds. Since, as is well known, likedissolves like, essential oil components can be selected according totheir similarity in structure to the odor to be reduced or eliminated.For example, if the odor is a hydrocarbon, then a hydrocarbon terpene,such as α-pinene, β-pinene, δ-3 carene, or dipentene, or mixturesthereof is preferred. If the odor is styrene, then terpenes such asp-cymene or p-cymenene are preferred for treating this odor. Similarly,essential oil components that reduce odors such as ammonia, sulfur andmercaptans can be readily selected. Where a broad spectrum of odors isto be treated, a broad-spectrum mix of essential oils and/or essentialoil components can be used, thus combining the reactivity of a number ofcomponents.

One preferred odor reducing additive is a broad spectrum mixture ofcomponents and/or essential oils and includes:

Concentration Oil/terpene range (%) Rosemary oil 10–20 Cedarwood oil 8–12 Pine Needle oil 20–30 Eucalyptus oil 10–20 Clove oil  5–10 Thymeoil  8–12 Vetiver oil 1–6 Vanilla oleoresin 1–6 Lavender oil  5–10 TeaTree oil 3–7

Another preferred odor reducing additive includes:

Concentration Oil/terpene range (%) α-pinene 2–7 β-pinene 2–7 d 3 carene2–7 dipentene 15–25 p-cymene  5–15 cineole  5–15 camphor 10–20 terpineol 7–13 bornyl acetate 2–6 cedrene 2–6 cedrol  5–10 thymol 2–16

Another preferred odor reducing additive that is especially useful forreducing or eliminating hydrocarbon odors is one or more terpenes,selected from d-limonene, l-limonene, dl-limonene, pinene, carene,terpinolene, camphene, myrcene, and sabinene, or essential oilscontaining such terpenes such as Eucalyptus, Pine, Pine needle,Turpentine, or mixtures thereof.

Another preferred odor reducing additive comprises as primaryconstituents: (+) limonene, pine extract and pine white oil, pinussylvestris oil, anise seed oil, and clove bud oil. The additive maycontain additional miscellaneous oils including aniseed oil, camphorwhite oil, cedarwood atlas oil, cedarwood texas oil, cedarwood virginiaoil, lavandin absolute, lime distilled oil, olibanum extract, rosemaryoil, sandlewood west indian oil, tocopherol alpha, and vanilla.Preferably, these components are present at a volume ratio of about35–45% of (+) limonene, about 25–35% of pine extract and pine white oil,about 1–5% pinus sylvestris oil, about 3–8% anise seed oil, about 3–8%clove bud oil and about 20–25% miscellaneous oils. This additive ispreferred for reducing odor where the oil based medium is liquid asphaltcement.

For effective odor treatment, the amount of odor reducing additive thatis added to oil based media will depend on several factors includingwhether isolated essential oil components or essential oils are used,the concentration of components in the essential oils, the quantity ofvolatiles in the oil based media that cause the odor, and the cost ofthe particular component(s) or essential oil(s). As a general guideline,it is preferred that about 0.0001 to about 10%, more preferably about0.0003% to about 3%, by volume, of odor reducing additive is used,relative to the volume amount of oil based media.

The odor reducing additive can be added directly to an odor producingoil based medium, or it can be diluted with a carrier oil. Dilution witha carrier oil is especially useful where only a very small amount ofadditive is required to reduce odor, thereby facilitating handling ofthe additive. Dilution with a carrier oil can also help dissolve ordisperse the additive in the oil based medium. Suitable carrier oilsinclude, for instance, mineral oil, vegetable oil, fatty acid alkylesters, or mixtures thereof.

A preferred carrier oil is fatty acid alkyl esters or mixtures of fattyacid alkyl esters. Preferably, the fatty component of the fatty acidester is linear or branched C₈–C₂₀ alkyl. Preferably the alkyl componentof the fatty acid ester is linear or branched C₁–C₆ alkyl. Preferredcarrier oils includes fatty acid methyl ester(s) and fatty acid ethylesters. Preferred oils also include methyl and ethyl esters of palm,coconut, canola, peanut, sunflower, and safflower oils. Anotherpreferred carrier oil is SOYGOLD® 1000, which contains alkyl C₁₆–C₁₈methyl esters, and is a methyl ester of soybean oil. SOYGOLD® 1000 isavailable from AG Environmental Products L.L.C., Lenexa, Kans.

When diluted with a carrier oil, it is preferred that the ratio of odorreducing additive to carrier oil is about 1–50% by volume of odorreducing additive and about 50–99% by volume of carrier oil.

Oil based media with which the odor reducing additives of the inventioncan be used include all oil based media that produce odors. Examples ofsuch media include, but are not limited to, wax based products such ascandles, resins, fuel oil, waste oil fuel oil, synthetic lubricants,rubber, liquid asphalt cement, and hot mix asphalt. Preferred oil basedmedia include wax based products, liquid asphalt cement, hot mix asphaltand waste oil fuel oil.

When added to wax based products, such as candles, the odor reducingadditives of the invention function to reduce or eliminate odors in thearea surrounding the location where the candle is being burned. Thus,burning of a candle containing the odor reducing additive of theinvention reduces odors in the surroundings of the candle. It ispreferred that the odor reducing additive is diluted with carrier oilprior to addition of the additive to the wax. Preferably, the ratio isabout 35 to about 45 volume % of additive to about 55–65% by weight ofcarrier oil. Preferably, the total amount of odor reducing additive andcarrier oil that is mixed with the wax is about 10 to about 15% based onthe volume of the wax.

As indicated above, another preferred oil based medium is hot mixasphalt. Generally, hot mix asphalt contains at least two majorcomponents; liquid asphalt cement (“liquid AC,” also known as “binder”)and aggregates. The liquid AC functions to coat and bind together theaggregate particles. The aggregates provide stability and strength tothe asphalt mixture. Aggregates can be, for example, crushed rock,fillers, gravel, stone, quarry gravel and recycled paving material.

It is preferred that the odor reducing additive used with hot mixasphalt is first diluted with a carrier oil, such as fatty acid alkylesters, prior to addition to the asphalt. Preferably, the ratio ofadditive to carrier oil is about 1–5% by volume of additive to about95–99% by volume of carrier oil.

Preferably, the diluted additive is mixed with the liquid AC prior tomixing of the liquid AC with the aggregates. Thus, for example, thediluted additive is mixed with the liquid AC during or after refinementof the liquid AC from crude oil, or at a liquid AC terminal, or at ahotmix asphalt plant prior to mixing of the liquid AC with aggregates.

For effective odor reduction, it is preferred that the ratio of thetotal amount of odor reducing additive and carrier oil that is mixedwith the liquid AC is about 0.001 to about 0.05% of additive and carrieroil to about 99.999–99.95% by volume of liquid AC. More preferably, theratio is about 0.007–0.03% of additive and carrier oil to about99.993–99.97% by volume of liquid AC. Even more preferably, the ratio isabout 0.009–0.02% of additive and carrier oil to about 99.991–99.98% byvolume of liquid AC.

The following examples are illustrative of the invention, but do notserve to limit its scope.

EXAMPLES

The examples demonstrate the capability of the odor reducing additivesof the invention to reduce odor of asphalt. In these examples, odorreducing additives were mixed with asphalt in sealed vials. Theheadspace of the sealed vials was evaluated by gas chromatography/massspectroscopy (GC/MS). GC/MS data indicated that the headspace of asphaltsamples containing odor reducing additives contained reduced amounts ofoil volatiles compared to the headspace of asphalt samples notcontaining odor reducing additives.

General Provisions

Instrumentation: HP 5890 gas chromatograph attached to an HP 5970 MSD

Inject temperature 250° C.

Detector temperature 280° C.

Oven Equilibrium time 0.50 minutes

Initial temperature 70° C.

Initial time 2.00 minutes

Change level 1 to level 2 20° C./min

Final temperature 210° C.

Transfer line temperature 300° C.

Odor reducing additive X contains Thyme, Cinnamon, Pine Needle, Pinewood, Aniseed, Lemon, the reaction product of turpentine oil and acidand subsequent fractionation, and orange oil. The additive is dilutedwith carrier oil at a volume ratio of about 3% additive to about 97% ofcarrier oil.

Odor reducing additive Y contains (+) limonene, pine extract, pine whiteoil, pinus sylvestris oil, anise seed oil, clove bud oil and othermiscellaneous oils. The additive is diluted with carrier oil at a volumeratio of about 3% additive to about 97% of carrier oil.

Example 1

Asphalt samples, labeled PG70-22 and 64-22, were heated until theybecame a viscous liquid. Approximately 5.0 g of each of the two asphaltsamples were added to separate 20 mL vials. Vials were labeled 6422-1,6422-2, 6422-3, 7022-1, 7022-2 and 7022-3. Vials were allowed to come toroom temperature. One μL of odor reducing additive X was added to eachof the 6422-2 and 7022-2 vials. One μL of odor reducing additive Y wasadded to each of the 6422-3 and 7022-3 vials. Individual vials, crimpedshut using Teflon faced septa and aluminum seals, were placed in aFisher forced air oven and heated at 151° C. for 30 minutes after which1 mL of headspace of each vial was injected into a GC/MS system. A blankconsisting of an empty crimped vial was also analyzed using identicalprocedures.

A large peak was found at a retention time of 4.7 minutes (FIG. 1). Thissubstance, also found in the blank, was found to be a volatile substancegiven off by septa when heated to 151° C. and the Teflon face penetratedby the injection needle.

Asphalt sample 6422 in addition to the 4.7 peak, produced a series ofincreasing molecular weight hydrocarbon components with retention timessimilar to a fractional distillation pattern (FIGS. 2 and 3). Eight ofthe major peaks were selected; their integrated areas obtained andcorrected areas calculated by normalizing factor needed to adjust allsample sizes to a value of 5.0 g. An average normalized total peak areaequaled 14,266+/−5% counts.

Vial 6422-1 had an average normalized total peak area of 14,266+/−5%counts.

Vial 6422-2 (containing 1 μL of X oil) had an average normalized totalpeak area of 14,735+/−5% counts (FIG. 4).

Vial 6422-3 (containing 1 μL of Y oil) produced no detectablehydrocarbon peaks (FIG. 5). Three aliquot samples of 6422-3 were runwith identical results. (Minimum detection limit was approximately 500counts).

Vial 7022-1 had an average normalized total peak area of 1494+/−5%counts. (FIG. 6).

Vial 7022-2 (containing 1 μL of X oil) produced no detectablehydrocarbon peaks. (FIG. 7). Three aliquot samples of 7022-2 were runwith identical results. (Minimum detection limit was approximately 500counts).

Vial 7022-3 (containing 1 μL of Y oil) produced no detectablehydrocarbon peaks (FIG. 8). Three aliquot samples of 7022-3 were runwith identical results. (Minimum detection limit was approximately 500counts).

These data show that the combination of essential oils and methyl esterof soybean oils in the additive samples tested are useful at reducingodor.

1. A method for reducing odor in oil based media, the method comprisingmixing an odor reducing amount of an odor reducing additive with an oilbased medium, wherein the oil based medium is resins, fuel oil, wasteoil fuel oil, synthetic lubricants, rubber, liquid asphalt cement, orhot mix asphalt and wherein the odor reducing additive comprises (+)limonene, pine extract and pine white oil, pinus sylvestris oil, aniseseed oil, and clove bud oil.
 2. The method of claim 1 wherein the odorreducing additive is diluted with a carrier oil.
 3. The method of claim1 wherein the odor reducing additive further comprises aniseed oil,camphor white oil, cedarwood atlas oil, cedarwood texas oil, cedarwoodvirginia oil, lavandin absolute, lime distilled oil, olibanum extract,rosemary oil, sandlewood west indian oil, tocopherol alpha, and vanilla.4. The method of claim 1 wherein the oil based medium is hot mixasphalt.
 5. A mixture having reduced odor comprising: an oil basedmedium; and an odor reducing additive, wherein the oil based medium isresins, fuel oil, waste oil fuel oil, synthetic lubricants, rubber,liquid asphalt cement, or hot mix asphalt and wherein the odor reducingadditive comprises (+) limonene, pine extract and pine white oil, pinussylvestris oil, anise seed oil, and clove bud oil.
 6. The mixture ofclaim 5 wherein the odor reducing additive is diluted with a carrieroil.
 7. The mixture of claim 6 wherein the carrier oil is fatty acidalkyl esters.
 8. The mixture of claim 5 wherein the odor reducingadditive further comprises aniseed oil, camphor white oil, cedarwoodatlas oil, cedarwood texas oil, cedarwood virginia oil, lavandinabsolute, lime distilled oil, olibanum extract, rosemary oil, sandlewoodwest indian oil, tocopherol alpha, and vanilla.
 9. The mixture of claim5 wherein the oil based medium is liquid asphalt cement.
 10. The mixtureof claim 9 further comprising an aggregate.
 11. The mixture of claim 10wherein the aggregate is selected from the group consisting of crushedrock, fillers, gravel, stone, quarry gravel and recycled pavingmaterial.
 12. Asphalt having reduced odor comprising: liquid asphaltcement; and an odor reducing additive, wherein the odor reducingadditive comprises (+) limonene, pine extract and pine white oil, pinussylvestris oil, anise seed oil, clove bud oil, aniseed oil, camphorwhite oil, cedarwood atlas oil, cedarwood texas oil, cedarwood virginiaoil, lavandin absolute, lime distilled oil, olibanum extract, rosemaryoil, sandlewood west indian oil, tocopherol alpha, and vanilla.
 13. Acandle composition, comprising: candle wax; and an odor reducingadditive, wherein the odor reducing additive comprises (+) limonene,pine extract and pine white oil, pinus sylvestris oil, anise seed oil,and clove bud oil.
 14. The candle composition of claim 13 wherein theodor reducing additive is diluted with a carrier oil.
 15. The candlecomposition of claim 13 wherein the odor reducing additive furthercomprises aniseed oil, camphor white oil, cedarwood atlas oil, cedarwoodtexas oil, cedarwood virginia oil, lavandin absolute, lime distilledoil, olibanum extract, rosemary oil, sandlewood west indian oil,tocopherol alpha, and vanilla.
 16. A method for reducing or eliminatingodor, the method comprising burning the candle composition of claim 13,wherein the odor is reduced or eliminated in the area surrounding thecandle.